WO2020096071A1 - Coating material and film - Google Patents

Abstract

The purpose of the present invention is to provide products, in particular, a coating material, capable of preventing icing and/or snow accretion. The coating material comprises a first oil ingredient, a second oil ingredient, and a first resin precursor, which is a precursor of a resin ingredient. Curing the first resin precursor which contains the first and second oil ingredients gives an oil-containing resin layer comprising the first and second oil ingredients and the resin ingredient. The second oil ingredient constitutes a low-temperature separable oil ingredient which, when the temperature declines to or below a given value, can separate from the first-oil-ingredient phase to ooze out of the oil-containing resin layer.

Description

Paints and films

The present invention relates to a paint, particularly a paint and a film capable of preventing icing and / or snow accretion.

Several products have been developed that can prevent icing and snow on various structures such as house roofs, power lines, mats, vehicles, and ships.

For example, Japanese Unexamined Patent Publication No. 7-148879 (Patent Document 1) discloses an ice-and-snow adhesion preventing sheet that can prevent ice-and-snow adhesion to various structures in cold regions. This sheet comprises a heat-insulating layer made of a sponge material and a surface layer laminated on the heat-insulating layer, the surface layer being made of rubber or resin dispersed so that an oil agent can bleed on the surface. Has been done. The oil agent is held in the surface layer and constantly bleeds onto the surface of the surface layer. On the other hand, in order to prevent remarkable bleeding out of the oil agent, the viscosity of the oil agent is set to a value equal to or higher than a predetermined value here to maintain the effect of preventing snow from adhering to the snow for as long as possible.

Japanese Unexamined Patent Publication No. 2003-328308 (Patent Document 2) discloses a rubber mat that can prevent ice and snow from sticking. This rubber mat is made of a synthetic rubber having a predetermined hardness, and is configured such that a liquid additive having an effect of preventing snow from adhering to the surface bleeds under the condition that the temperature is 5 ° C. or less. In order to adjust the bleed amount of the liquid additive, the amount of the liquid additive with respect to the rubber of the rubber mat is adjusted within a predetermined range here.

Japanese Patent No. 6245714 (Patent Document 3) discloses a wet gel which has poor adhesion to ice and is capable of spontaneous syneresis by temperature or chemical reaction. This wet gel can be mixed with the crosslinked silicone resin in which the silicone resin composition is cured, the first liquid capable of dissolving the silicone resin composition, and the first liquid ( That is, when the second liquid and the first liquid are mixed, a transparent mixed solution is formed without phase separation) The second liquid is included. However, the first liquid may also serve as the second liquid.

JP-A-7-148879 JP-A-2003-328308 Patent No. 6245714

However, with the configuration described in Patent Document 1, it is difficult to obtain the effect of preventing the adhered snow from adhering for a long period of time because the oil agent continues to bleed regardless of the temperature. Further, while the oil agent may bleed excessively, when the viscosity of the oil agent is set too high, bleeding may not be performed smoothly. Further, since all the oil agents dispersed in the surface layer can be bleed, there is a possibility that the oil agents may excessively bleed.
Further, in the configuration described in Patent Document 2, although the bleeding amount of the liquid additive can be controlled depending on the temperature condition, all the liquid additive added to the rubber of the rubber mat can be bleeding, The liquid additive may bleed excessively.
Furthermore, the structure described in Patent Document 3 is a wet gel, and is not intended for outdoor use where strength is required, and there is a problem that the strength is insufficient. Further, since the first liquid and the second liquid are miscible, and the first liquid may also serve as the second liquid, the first liquid and the second liquid are the same. At times, there is a risk of excessive syneresis.
The present invention has been made to solve these problems in the prior art, and an object of the present invention is to provide a product having an improved function of preventing ice formation and / or snow accumulation, particularly a paint and a film. ..

In order to solve the above problems, a paint according to an aspect of the present invention includes a first oil component, a second oil component, and a first resin precursor that is a precursor of a resin component, And a coating composition for forming an oil-containing resin layer containing the first and second oil components and the resin component by curing the first resin precursor containing the second and oil components. The second oil component is characterized in that it constitutes a low temperature phase-separable oil component that can be phase-separated from the first oil component and exude from the oil-containing resin layer when the temperature drops below a predetermined value. .. The predetermined value may be a freezing point.
The paint according to this one aspect enables use in a flexible aspect. In addition, the oil component exuding from the oil-containing resin layer is a low-temperature exuding oil component that can exude when the temperature falls below a predetermined value, so that it does not bleed wastefully and bleeds when necessary. Thus, for example, it is possible to more reliably prevent the accretion of icing snow. Furthermore, since this oil component is a part of the oil component contained in the oil-containing resin layer, the oil component will not be excessively bleed.

In the coating composition according to the above aspect, the first and second oil components are a solubility parameter value (SP value) of a resin component of the oil-containing resin layer formed by curing the first resin precursor. The difference from the value of the solubility parameter of the first oil component is smaller than the difference between the value of the solubility parameter (SP value) of the resin component of the oil-containing resin layer and the value of the solubility parameter of the second oil component. Is preferred.

Further, in the coating material of the above aspect, the first resin precursor may be a moisture-curable type that is cured by moisture, or an ultraviolet-curable type that is cured by ultraviolet irradiation, or by heating. It may be a thermosetting type that hardens, or may be a type that hardens by adding a curing agent that causes a crosslinking reaction with the first resin precursor, or the first resin precursor of the coating composition. It may be a combination with a liquid curing agent that cures the first resin precursor by a crosslinking reaction with.

Furthermore, in the coating material of the above aspect, it is preferable that the resin component of the oil-containing resin layer is contained in an amount of 25 wt% or more based on the total weight of the oil-containing resin layer.

In addition, in the paint of the above aspect, it is preferable that the second oil component is contained in a proportion of 3 wt% or more based on the weight of the entire oil-containing resin layer.

Moreover, in the coating material of the above aspect, a second resin precursor that forms a surface resin layer by being cured on the oil-containing resin layer formed by curing the first resin precursor. The surface resin layer can further allow the low temperature phase-separable oil component exuded from the oil-containing resin layer to penetrate to the surface of the surface resin layer on the side opposite to the oil-containing resin layer. It may have oil permeability.

Further, in the coating material according to the above aspect, it is preferable that the surface resin layer has higher abrasion resistance than the oil-containing resin layer.
Further, in the coating material of the above aspect, the amount of surface oil at −20 ° C. is preferably 40 μg / cm 2 or more.
Further, in the coating material of the above aspect, it is preferable that the difference in the solubility parameter between the first oil component and the resin component of the oil-containing resin layer is within 0.6 (J / cm ³ ) ^1/2 .

In the coating material of the above aspect, the solubility parameter value (SP value) of the oil-containing resin layer formed by curing the first resin precursor and the solubility parameter value (SP of the second oil component (SP value) It is preferable that the wetting parameter, which is obtained by the absolute value of the difference with the value), is 1.5 (J / cm ³ ) ^1/2 or less.
Further, in the paint according to the above aspect, it is preferable that the oil-containing resin layer formed by curing the first resin precursor have a solubility parameter contribution value of 0.1 or more.

In order to solve the above problems, a film according to one aspect of the present invention is a film including an oil-containing resin layer containing first and second oil components, and the second oil component has a temperature of a predetermined value. It is characterized in that it comprises a low temperature phase-separable oil component that can be phase-separated from the first oil component and exude from the oil-containing resin layer when the temperature decreases below.

INDUSTRIAL APPLICABILITY According to the present invention, a product capable of preventing icing and / or snow accretion, in particular, can be used in a flexible manner as compared with a sheet or the like having a physically defined shape from the beginning of use. Paints and films are provided.

It is a figure which shows the oil-containing resin layer formed from the coating material with one Embodiment of this invention with a structure. It is a figure which shows the layer structure containing the surface resin layer formed from the coating material by one Embodiment of this invention with a structure. It is the optical microscope image which image | photographed the oil state which appeared on the surface of the oil-containing resin layer. It is a schematic diagram of a testing machine used for an abrasion resistance test.

Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

1. Kind of paint (1) First paint The first paint contains a first resin precursor which is a precursor of a resin component and two kinds of oil components, that is, a first oil component and a second oil component. .. The oil-containing resin layer 11 is formed by curing the first resin precursor containing the first oil component and the second oil component. The oil-containing resin layer 11 contains a first oil component, a second oil component, and a resin component, and a part of the contained oil, particularly the second oil component, can be exuded (bleed) from the resin component. The solid resin layer prevents the icing and / or snowing by the exuded second oil component.

FIG. 1 shows an oil-containing resin layer 11 formed by applying and curing the first paint together with the structure 10. The layer thickness of the oil-containing resin layer 11 is substantially determined by the thickness of the applied first coating material. Although not particularly limited, it is preferably 10,000 μm or less in order to properly exude oil, and from the viewpoint of strength, it is preferably 10 μm or more.

<First resin precursor>
The first resin precursor is a precursor that constitutes the resin component of the oil-containing resin layer 11, and is a moisture-curable type that cures with moisture, an ultraviolet-curable type that cures with ultraviolet irradiation, and a thermoset that cures with heating. It may be of any type. Further, it may be cured by adding a curing agent that causes a crosslinking reaction with the first resin precursor. Furthermore, a coating material that is cured by adding a curing agent that causes a crosslinking reaction with the first resin precursor, and a curing reaction of the first resin precursor by performing a crosslinking reaction with the first resin precursor of the coating material, It may be a combination with a liquid curing agent.

The first resin precursor is not particularly limited, but for example, silicone resin, polyurethane resin, polyurethane acrylic resin, vinyl chloride resin, polyester resin, elastomers, fluorine resin, polyamide resin, polyolefin resin (polyethylene, polypropylene, etc.) , Acrylic resins, and the like. Among them, silicone resins are preferable from the viewpoints of excellent bleeding effect of oil components and excellent outdoor exposure durability.

As the silicone resin, any appropriate silicone resin can be adopted as long as the effect of the present invention is not impaired. Only one type of silicone resin may be used, or two or more types may be used. Such silicone resin may be a condensation type silicone resin or an addition type silicone resin. The silicone resin may be a one-component type silicone resin (for example, a one-component type room temperature curable (RTV) resin) that is dried alone, or a two-component type silicone resin (eg, a one-component type). Two-part type room temperature curable (RTV) resin).

Examples of the silicone resin include 1-component RTV rubber manufactured by Shin-Etsu Chemical Co., Ltd. (for example, KE-3423, KE-347, KE-3475, KE-3495, KE-4895, KE-4896, KE-1830, KE-1884, KE-3479, KE-348, KE-4897, KE-498, KE-1820, KE-1825, KE-1831, KE-1833, KE-1885, KE-1056, KE-1151, KE- 1842, KE-1886, KE-3424G, KE-3494, KE-3490, KE-40RTV, KE-4890, KE-3497, KE-3498, KE-3493, KE-3466, KE-3467, KE-1862, KE-1867, KE-3491, KE-3492, KE-3417, KE- 418, KE-3427, KE-3428, KE-41, KE-42, KE-44, KE-45, KE-441, KE-445, KE-45S, etc.), Shin-Etsu Chemical Co., Ltd. RTV rubber (eg KE-1800T-A / B, KE-66, KE-1031-A / B, KE-200, KE-118, KE-103, KE-108, KE-119, KE-109E-A / B, KE-1051J-A / B, KE-1012-A / B, KE-106, KE-1282-A / B, KE-1283-A / B, KE-1800-A / B / C, KE -1801-A / B / C, KE-1802-A / B / C, KE-1281-A / B, KE-1204-A / B, KE-1204-AL / BL, KE-1280-A / B , KE-513-A / B, KE- 21-A / B, KE-1285-A / B, KE-1861-A / B, KE-12, KE-14, KE-17, KE-113, KE-24, KE-26, KE-1414, KE-1415, KE-1416, KE-1417, KE-1300T, KE-1310ST, KE-1314-2, KE-1316, KE-1600, KE-1603-A / B, KE-1606, KE-1222 A / B, KE-1241, etc.), Shin-Etsu Chemical Co., Ltd. silicone sealant (eg, KE-42AS, KE-420, KE-450, etc.), Shin-Etsu Chemical Co., Ltd. rubber compound (eg, KE- 655-U, KE-675-U, KE-931-U, KE-941-U, KE-951-U, KE-961-U, KE-971-U, KE-981- U, KE-961T-U, KE-971T-U, KE-871C-U, KE-9410-U, KE-9510-U, KE-9610-U, KE-9710-U, KE-742-U, KE-752-U, KE-762-U, KE-772-U, KE-782-U, KE-850-U, KE-870-U, KE-880-U, KE-890-U, KE- 9590-U, KE-5590-U, KE-552-U, KE-582-U, KE-552B-U, KE-555-U, KE-575-U, KE-541-U, KE-551- U, KE-561-U, KE-571-U, KE-581-U, KE-520-U, KE-530B-2-U, KE-540B-2-U, KE-1551-U, KE- 1571-U, KE-152-U, KE-174- , KE-3601SB-U, KE-3711-U, KE-3801M-U, KE-5612G-U, KE-5620BL-U, KE-5620W-U, KE-5634-U, KE-7511-U, KE -7611-U, KE-765-U, KE-785-U, KE-7008-U, KE-7005-U, KE-503-U, KE-5042-U, KE-505-U, KE-6801 -U, KE-136Y-U, etc., LIMS (Liquid Silicone Rubber Injection Molding System) manufactured by Shin-Etsu Chemical Co., Ltd. (for example, KEG-2000-40A / B, KEG-2000-50A / B, KEG-2000- 60A / B, KEG-2000-70A / B, KEG-2001-40A / B, KEG-2001-50A / B, KE-1950-10A / B, KE 1950-20A / B, KE-1950-30A / B, KE-1950-35A / B, KE-1950-40A / B, KE-1950-50A / B, KE-1950-60A / B, KE-1950- 70A / B, KE-1935A / B, KE-1987A / B, KE-1988A / B, KE-2019-40A / B, KE-2019-50A / B, KE-2019-60A / B, KE-2017- 30A / B, KE-2017-40A / B, KE-2017-50A / B, KE-2090-40A / B, KE-2090-50A / B, KE-2090-60A / B, KE-2090-70A / B, KE-2096-40A / B, KE-2096-50A / B, KE-2096-60A / B, etc.), LR7 manufactured by Asahi Kasei Wacker Silicone Co., Ltd. Examples include 665 series, LR3033 series manufactured by Asahi Kasei Wacker Silicone Co., Ltd., TSE3032 series manufactured by Momentive Co., Ltd., and Silgard 184 manufactured by Toray Dow Corning.

<Oil component>
As the first oil component, for example, silicone oil, fluorine oil, hydrocarbon oil, polyether oil, ester oil, phosphorus compound oil, mineral oil oil or the like can be used.
Examples of the silicone oil include silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. (for example, KF96L series, KF96 series, KF69 series, KF99 series, KF50 series, KF54 series, KF410 series, KF412 series, KF414 series, FL series, KF). -6000, KF-6001, KF-6002, KF-6003, etc.), silicone oil manufactured by Momentive Co., Ltd. (for example, Element14 * PDMS series, TSF404 series, TSF410 series, TSF4300 series, TSF431 series, TSF433 series, TSF437 series, TSF4420 series, TSF4421 series, etc.), silicone oil manufactured by Toray Dow Corning Co., Ltd. (for example, BY16-846 series, SF8416 series, SH200 series, SH203 series, SH230 series, SF8419 series, FS1265 series, SH510 series, SH550 series, SH710 series, FZ-2110 series, FZ-2203 series, etc.) Silicone manufactured by Asahi Kasei Wacker Silicone Co., Ltd. Oil (WACKER (registered trademark) SILICONE FLUID AK series, WACKER (registered trademark) SILICONE FLUID AP series, WACKER (registered trademark) SILICONE FLUID AR series, WACKER (registered trademark) SILICONE FLUID AS series, WACKER (registered trademark) TN series, WACKER (registered trademark) L series, WACKER (registered trademark ) AF series, etc.), and the like.

On the other hand, as the second oil component, for example, silicone oil, fluorine oil, hydrocarbon oil, polyether oil, ester oil, phosphorus compound oil, mineral oil oil or the like can be used.
Examples of the silicone oil include silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. (for example, KF96L series, KF96 series, KF69 series, KF99 series, KF50 series, KF54 series, KF410 series, KF412 series, KF414 series, FL series, KF). -6000, KF-6001, KF-6002, KF-6003, etc.), silicone oil manufactured by Momentive Performance Materials Japan LLC (eg Element14 * PDMS series, TSF404 series, TSF410 series, TSF4300 series, TSF431 series). , TSF433 series, TSF437 series, TSF4420 series, TSF4421 series, etc.), Toray Dow Konin Silicone oil manufactured by corporation (for example, BY16-846 series, SF8416 series, SH200 series, SH203 series, SH230 series, SF8419 series, FS1265 series, SH510 series, SH550 series, SH710 series, FZ-2110 series, FZ-2203 series. Etc.) Silicone oil manufactured by Asahi Kasei Wacker Silicone Co., Ltd. (WACKER (registered trademark) SILICONE FLUID AK series, WACKER (registered trademark) SILICONE FLUID AP series, WACKER (registered trademark) SILICONE FLUID AR series, WACKER (registered trademark) SILICONE FLUID AS) Series, WACKER (registered trademark) TN Series, WACKER (Registered trademark) L series, WACKER (registered trademark) AF series, etc.) and the like.

For the first oil component, the second oil component, and the resin component (first resin precursor) of the oil-containing resin layer 11, for example, a combination satisfying the following properties 1) and 2) is selected.

1) The first oil component and the second oil component have a temperature at which it is not necessary to exude the second oil component into the oil-containing resin layer 11, for example, 20 ° C to 80 ° C which is significantly higher than a predetermined value such as a freezing point. At room temperature, they are compatible with each other without phase separation, but under the temperature environment where it is necessary to exude the second oil component into the oil-containing resin layer 11, for example, a temperature environment below a predetermined value such as a freezing point. To separate.
2) The first oil component has a temperature at which it is not necessary to exude the second oil component to the oil-containing resin layer 11 and a temperature at which it is necessary to exude the second oil component to the oil-containing resin layer 11. Both have an affinity for the resin component of the oil-containing resin layer 11, while the second oil component, in the presence of the first oil component, causes the oil-containing resin layer 11 to contain the second oil component. The behavior is changed depending on whether it is a temperature at which exudation is not required or a temperature at which it is necessary to exude the second oil component into the oil-containing resin layer 11.
More specifically, the second oil component has a temperature at which it is not necessary to exude the second oil component into the oil-containing resin layer 11 when the first oil component is not present, and The second oil component does not have an affinity for the resin component of the oil-containing resin layer 11 at both temperatures that require exudation, in other words, it exudes from the resin component of the oil-containing resin layer 11. On the other hand, in the presence of the first oil component, the second oil component is compatible with the first oil component at a temperature at which it is not necessary to exude the second oil component into the oil-containing resin layer 11, so that the oil component It has an affinity for the resin component of the containing resin layer 11, in other words, does not exude from it, but at the temperature at which it is necessary to exude the second oil component to the oil containing resin layer 11, It is phase-separated from the first oil component and has no affinity for the resin component of the oil-containing resin layer 11, in other words, it functions as a low temperature phase-separable oil component that is phase-separated from the first oil component.

It is empirically known that the value of the dissolution parameter serves as a criterion for judging the easiness of mixing the solvent and the solute. The relationship between the first oil component, the second oil component, and the resin component of the oil-containing resin layer 11 (first resin precursor) described above is also related to the values (SP value) of their solubility parameters. Can be explained based on relationships. The Hansen solubility parameter is used herein as the solubility parameter. This value is the kind of molecular unit that constitutes the molecular structure of each component by performing Fourier transform nuclear magnetic resonance spectroscopy analysis on the first oil component, the second oil component, and the resin component of the oil-containing resin layer 11. And the molar ratio thereof, and the Hansen solubility parameter of each molecular unit type can be obtained by calculating a weighted average by the molar ratio. The Hansen solubility parameter of each molecular unit type can be obtained from the molecular group contribution method using the software "HSPiP, Hansen Solubility Parameters in Practice ver4" available from the link (https://hansen-solubility.com/). .. Specifically, each constituent unit of the target substance can be input by the SMILES notation, and the HSP value (Δ _d, Δ _p , δ _h ) of each unit can be calculated.

In order to maintain the above relationships 1) and 2), at least the difference between the solubility parameter value of the resin component of the oil-containing resin layer 11 and the solubility parameter value of the first oil component is the resin component of the oil-containing resin layer 11. It is preferable to set it so as to be smaller than the difference between the value of the dissolution parameter of and the value of the solubility parameter of the second oil component. In order to maintain the above relationships 1) and 2), the blending ratio is based on the total weight of the oil-containing resin layer that is finally formed, for example, the resin component is at least 25 wt% or more, and the first oil component is It contains at least 5 wt% or more and the second oil component in a ratio of at least 3 wt% or more. Further, the difference in the dissolution parameter between the first oil component and the resin component of the oil-containing resin layer 11 is preferably set within 0.6 (J / cm ³ ) ^1/2 .
More specifically, the resin component of the oil-containing resin layer 11 is preferably 30 wt% or more, more preferably 35 wt% or more, still more preferably 40 wt% based on the weight of the entire finally formed oil-containing resin layer. % Or more. The upper limit is not particularly limited and is appropriately set depending on the relationship with the oil component, but may be 70 wt% or less, for example.
The first oil component can be set to, for example, 10 wt% or more, 15 wt% or more, 20 wt% or more, based on the total weight of the finally formed oil-containing resin layer. The upper limit is not particularly limited, but can be preferably set to 65 wt% or less, for example, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less.
The second oil component is preferably 5 wt% or more, more preferably 10 wt% or more, still more preferably 15 wt% or more, based on the total weight of the finally formed oil-containing resin layer. The upper limit is not particularly limited, but it can be preferably set to 62 wt% or less, for example, 60 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less.

For example, when the above relationships 1) and 2) are satisfied, the second oil component is compatible with the first oil component at a temperature at which it is not necessary to exude the second oil component into the oil-containing resin layer 11. Therefore, it does not exude from the surface of the oil-containing resin layer 11, and on the other hand, when the temperature changes to require exuding the second oil component into the oil-containing resin layer 11, phase separation from the first oil component occurs. Then, it can function as a low-temperature exudation oil component that can exude (bleed) from the surface of the oil-containing resin layer 11.

In addition, the solubility parameter value (SP value) SP ₁ of the oil-containing resin layer formed by curing the first resin precursor and the solubility parameter of the second oil component represented by the following formula The wetting parameter “Z”, which is obtained by the absolute value of the difference from the value (SP value) SP ₂ , is preferably 1.5 (J / cm ³ ) ^1/2 or less.
The wetting parameter “Z” is more preferably 0.8 (J / cm ³ ) ^1/2 or less, further preferably 0.5 (J / cm ³ ) ^1/2 or less, and particularly preferably 0. It is 3 (J / cm ³ ) ^1/2 or less. The lower limit of Z is not particularly limited as long as it is a value higher than 0 (J / cm ³ ) ^1/2 , for example, 0.001 (J / cm ³ ) ^1/2 or more, and more preferably 0.01 (J / cm ³ ) ^1/2 or more. / Cm ³ ) ^1/2 or more can be set. When Z is in the above range, the wettability of the second oil component bleeding to the oil-containing resin layer to be formed becomes high, and even if the bleeding oil is small, it spreads efficiently on the surface of the oil-containing resin layer. Thereby, the effect of preventing icing can be expressed with a smaller amount of oil.
The value of the solubility parameter of the oil-containing resin layer and the value of the solubility parameter of the second oil component can be calculated by the method described above.

Further, it is preferable that the oil-containing resin layer formed by curing the first resin precursor has a solubility parameter contribution value “F” described later of 0.1 or more. It is more preferably 0.2 or more, still more preferably 0.3 or more, and particularly preferably 0.4 or more. The upper limit can be, for example, 3.0 or less, preferably 2.5 or less, more preferably 2.0 or less, and further preferably 1.5 or less. The solubility parameter contribution value “F” can be calculated by the method described later. F represents the degree of compatibility of the oil-containing resin layer, the larger the value, the more likely it becomes incompatibility, and if it is in the above range, the contained oil component is likely to bleed, and thus a high anti-icing effect is obtained. Can be expressed.

In addition, here, the difference between the value of the solubility parameter of the resin component of the oil-containing resin layer 11 and the value of the solubility parameter of the first oil component and the second oil component is set to a predetermined relationship, whereby the oil-containing resin layer 11 is formed. The part of the contained oil, in particular, the second oil component is exuded (bleed) to prevent icing and / or snow accretion, but the scope of the present invention is not limited to these embodiments. It is not limited to. For example, the compatibility can be similarly controlled by utilizing the difference in the molecular weight and the difference in the molecular structure between the first oil component and the second oil component, and the temperature of the second oil component can be lowered to a predetermined value or lower. At this time, it can be phase-separated from the first oil component and exude from the oil-containing resin layer.

As is clear from the above description, the first oil component and the second oil component do not have to be physically distinguished, and it is sufficient if they are distinguished from each other in terms of the function and action described above. Therefore, both the first oil component and the second oil component do not have to be composed of one oil component, and if the above conditions are satisfied, a plurality of oil components may be provided for each of the first oil component and the second oil component. The oil component may be included.

(2) Second paint The second paint contains at least a second resin precursor which is a precursor of the resin component. Further, like the first paint, it may contain two kinds of oil components, that is, a third oil component and a fourth oil component. After forming the oil-containing resin layer using the first paint, applying the second paint on the oil-containing resin layer and curing the second resin precursor, or the third oil. By curing the second resin precursor containing the component and the fourth oil component, the surface resin layer 12 containing at least the resin component and further containing the third oil component and the fourth oil component is formed. can do. Here, the third oil component and the fourth oil component do not necessarily have to be included in the second paint, and may be included in the first paint. Therefore, the use of the third oil component and the fourth oil component in the second paint is optional.

The surface resin layer 12 that can be formed using the second paint can be provided in a state of being laminated on one surface of the oil-containing resin layer 11 for the purpose of protecting the surface of the oil-containing resin layer 11. It is a solid resin layer. The surface resin layer 12 is optionally provided to protect the surface of the oil-containing resin layer 11, and thus the use of the second coating material is optional. Since the surface resin layer 12 is disposed on the surface of the oil-containing resin layer 11, the second oil component accumulated in the oil-containing resin layer 11 does not hinder the function of preventing ice formation and / or snow formation. In addition, the surface resin layer 12 allows the second oil component exuded from the oil-containing resin layer 11 to penetrate to the surface of the surface resin layer 12 on the opposite side of the oil-containing resin layer 11 even when the oil-containing resin layer 11 is covered. It has oil permeability.

FIG. 2 shows, together with the structure 10, a layer structure including a surface resin layer 12 formed by applying a second coating material on the oil-containing resin layer 11 and curing the second coating material. The structure 10 is arranged on the other surface of the oil-containing resin layer 11 opposite to the one surface on which the surface resin layer 12 is laminated.

Although not particularly limited, the same material as the first resin precursor of the first paint can be used as the second resin precursor, and the first oil of the first paint can be used as the third oil component. The same material as the oil component can be used, while the same material as the second oil component of the first paint can be used as the fourth oil component.

The third oil component, the fourth oil component, and the resin component (second resin precursor) of the surface resin layer 12 are the first oil component, the second oil component, and the oil-containing resin layer 11 of the first coating material. Like the resin component (first resin precursor), it has the properties of 1) and 2) above. Therefore, like the first paint, the blending ratio is based on the weight of the entire surface resin layer to be finally formed, at least 25 wt% or more of the resin component and at least 5 wt% or more of the third oil component, The fourth oil component is contained in a proportion of at least 3 wt% or more, and other preferable values and the like are the same as those of the first oil component and the like of the first paint. However, since the surface resin layer 12 is provided for the purpose of protecting the surface of the oil-containing resin layer 11, it preferably has higher abrasion resistance than the oil-containing resin layer 11. In this case, since the abrasion resistance is improved more than that of the oil-containing resin layer 11, the proportion of the second resin precursor in the second coating is smaller than that of the first resin precursor in the first coating. Is also set to a significantly large value. For example, it is preferable that the resin component is 30 wt% or more, while the third oil component is 20 wt% and the fourth oil component is 10 wt% based on the total weight of the finally formed surface resin layer. ..

(3) Film The film may be formed by pre-curing the first coating material or the first coating material and the second coating material in a state of forming a thin film of 10 to 1000 μm. In this case, a film can be attached to various structures or the like instead of applying the paint. Like the paint, the film has an oil-containing resin layer containing first and second oil components, and the second oil component is phase-separated from the first oil component when the temperature drops below a predetermined value. Function as a low temperature phase-separable oil component that can be exuded from the oil-containing resin layer. As the resin component forming the oil-containing resin layer, for example, a resin obtained by crosslinking reaction of the first resin precursor described in “<First Resin Precursor>” can be suitably used, Preferred is a crosslinked silicone resin. As the first and second oil components, the above-mentioned “<oil component>” can be used. Further, the blending ratio of each component is designed in the same manner as described above. Thus, the first paint and the second paint can also be used to provide a film.

2. Examples, etc. Hereinafter, the first coating material for forming the oil-containing resin layer will be described more specifically with reference to examples and the like, but the invention is not limited to the following examples. is not.

[Example 1]
The first paint was prepared by the following method.
1) First Resin Precursor As the first resin precursor, dimethylpolysiloxane rubber (Sylgard 184 manufactured by Dow Corning Toray Co., Ltd.) was used. This rubber is cured by heating (see also Table 3 below).

2) Oil component Dimethylsiloxane oil (product number KF-96-100CS manufactured by Shin-Etsu Silicone Co., Ltd.) was used as the first oil component, and methylphenylsiloxane oil (TSF437 manufactured by Momentive Co.) was used as the second oil component. (See also Table 3 below).

3) Mixing The first resin precursor of 1) and the first oil component and the second oil component of 2) are mixed under the condition of 25 ° C. and 101 kPa, and the mixed liquid is spun at a speed of about 120 rpm. Then, the mixture was stirred for 60 seconds, and then the mixture was further stirred for 60 seconds and defoamed for 60 seconds with a rotation / revolution mixer (CONDITIONING MIXER AR-250 manufactured by Shinky Co., Ltd.) to obtain a first paint. The blending ratio was 60 wt% for the resin component, 23 wt% for the first oil component, and 17 wt% for the second oil component, based on the total weight of the finally formed oil-containing resin layer.

The first coating material obtained by the above method was applied onto a PET film (Lumirror S10 # 125 manufactured by Toray Industries, Inc.) and heat-cured at 100 ° C. for 3 hours to contain an oil having a thickness of about 140 μm. A resin layer was formed, and the oil-containing resin layer was evaluated as follows. Here, the value of the solubility parameter of the first oil component dimethylsiloxane oil is 11.7 (J / cm ³ ) ^1/2 , and the value of the solubility parameter of the second oil component methylphenylsiloxane oil is 13.9 ( J / cm ³ ) ^1/2 , and the dimethylpolysiloxane rubber as a resin component formed by curing the first resin precursor has a solubility parameter value of 11.9 (J / cm ³ ) ^{1 / Is 2} .

5) Evaluation <layer thickness>
A film thickness meter MFC-101 (manufactured by Nikon) was used for measuring the layer thickness.
Although not particularly limited, when the surface resin layer is provided, the layer thickness of the surface resin layer is set so that the oil can easily permeate to the surface of the surface resin layer, in other words, the oil permeability to the surface resin layer is ensured. Therefore, it is preferably 75% or less of the oil-containing resin layer, more preferably 50% or less, and further preferably 35% or less. Further, depending on the resin component of the surface resin layer, from the viewpoint of strength, it is preferably 5% or more of the oil-containing resin layer, more preferably 20% or more, and further preferably 30% or more. preferable.

<Phase separation and compatibility>
a) Phase separation and compatibility depending on temperature changes between the "first oil component" and the "second oil component", b) "first oil component" and "resin component of oil-containing resin layer" Affinity according to temperature change between the two, and c) Affinity according to temperature change between the "second oil component" and the "resin component of the oil-containing resin layer" were evaluated. However, direct analysis targets are a mixture of the “first oil component” and the “second oil component” extracted from the oil-containing resin layer, and the oil component bleeding from the surface of the oil-containing resin layer.
In order to evaluate the above a), first, the oil-containing resin layer was immersed in toluene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) at 20 ° C. for 24 hours to extract the first oil component and the second oil component as a mixture. .. The first oil component and the second oil component in the mixture were separated using liquid layer chromatography. With respect to the extracted mixture of the first oil component and the second oil component, "transmittance at 20 ° C and 500 nm" and "transmittance at 3 ° C and 500 nm" were measured, and the difference between them was measured at "20 ° C and 500 nm. Based on the ratio of the "rate", it was determined whether "phase separated (not compatible)" or "compatible (not phase separated)". More specifically, when the difference is 10% or more, it is evaluated as "phase separated according to temperature change (not compatible)", and when the difference is less than 10%, "temperature change" According to the above, they are compatible (no phase separation). " An ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, V-750) was used to measure the transmittance, the measurement wavelength was 500 nm, the scan speed was 1000 nm / min, the stirring speed was 400 rpm, and the temperature was 20 ° C or 3 ° C. The measurement was performed after the temperature was set at 0 ° C. and the sample was left standing for 10 minutes. The reference was the atmosphere.
The evaluation criteria are as follows.
◯: 10% or more ×: Less than 10% For the above b) and c), the oil-containing resin layer containing only each oil component was added to the oil-containing resin layer from which the oil component was extracted. It was evaluated by whether or not the first oil component and the second oil component bleed from the surface of the oil-containing resin layer under the environment of 0 ° C. and under the environment of 3 ° C., respectively.
The evaluation criteria are as follows.
◯: Bleed at both 20 ° C and 3 ° C ×: Neither bleed at 20 ° C nor 3 ° C

<Amount of surface oil>
The measurement target is the amount of oil bleeding on the surface of the oil-containing resin layer at 20 ° C., the freezing point of 0 ° C., and −20 ° C., respectively. During the measurement, it was confirmed that the bleeding oil was mainly the second oil component. FIG. 3 shows an example of an optical microscope image of a state of oil bleeding on the surface of the oil-containing resin layer.
The amount of surface oil is measured by the following method.
When the oil-containing resin layer cut into a size of 10 cm × 2 cm near the center was left at 20 ° C., 0 ° C., and −20 ° C. for 16 hours, the oil bleeding on the surface of the oil-containing resin layer was removed. Under a temperature environment of 20 ° C, 0 ° C, and -20 ° C, collect with a cell scraper (Kennis Co., Ltd., CSS-10) until the oil does not show any change in weight (oil absorption). Suck up. Oil collection with a cell scraper and absorption of oil removal paper are repeated 7 times per minute. The difference in weight of the oil removing paper before and after oil absorption was defined as the amount of surface oil. The test was performed 3 times, and the average value was calculated.
The evaluation criteria are as follows.
◎ ・ ・ ・ 300 μg / cm ² or more ○ ・ ・ ・ 40 μg / cm ² or more and less than 300 μg / cm ² × ・ ・ ・ less than 40 μg / cm ^{2 In} order to prevent wasteful bleeding, the surface oil amount is 40 μg / cm at 20 ° C. ^It is preferably less than ^2, more preferably 40 μg / cm ² or more, and more preferably 300 μg / cm ² or more at 0 ° C. and −20 ° C., in order to prevent snow accretion. However, even at 20 ℃ 40μg / cm ² or more, even 40 [mu] g / cm ² or less at 0 ℃ and -20 ° C., is sometimes available.

<Abrasion resistance>
The abrasion resistance of the oil-containing resin layer was evaluated.
A Gakushin abrasion tester ((model number: RT-300S, Daiei Kagaku Seiki Seisakusho) was used as a measuring device. A schematic diagram of the tester is shown in Fig. 4. The tester 2 includes a test stand 21 and screws. A support plate 22 fixed to the test table 21 by 22a and the like, and friction disposed above the support body 22 and below the cantilever-shaped load arm 24 loaded by the weight 23. The child 25 (size: 2 cm × 2 cm) is provided with the test piece 32 of the test piece 2 attached on the support plate 22 via the adhesive material 31 (Nitto Denko No. 5000NS). For the oil-containing resin layer, in particular, for the area of 20 mm × 120 mm, a water resistant abrasive 34 having a # 120 roughness was attached to the lower side of the friction element 25 via the pressure-sensitive adhesive 31 as a weight 23. 125g / cm ² adjusted by load arm 24 The reduction rate of the oil-containing resin layer was calculated when the blade was reciprocated 30 times at a pressing force of 100 mm / s per second, and the room temperature was set to 20 ° C.
The evaluation criteria are as follows.
◎ ・ ・ ・ less than 50% ◯ ・ ・ ・ 50% or more and less than 80% × ・ ・ ・ 80% or more The wear resistance is preferably less than 80%, more preferably less than 50%, and further preferably less than 35%. However, it may be usable even at 80% or more.

<Icing power>
The object to be measured is the force required to move the ice blocks iced on the oil-containing resin layer in the environment of −20 ° C. For convenience, in the present specification, the magnitude of this force is referred to as “icing force”. It was defined as.
The icing force is measured by the following method.
1. First, a column-shaped ice mass is prepared. For the ice block, place a stainless steel ring (inner diameter 25 mm) on the bottom of a styrene square case 16 type (made by AS ONE), pour 6 g of pure water into it and freeze at -20 ° C for 16 hours or more, and remove the stainless steel ring after freezing. It is made by doing.
2. Then, the film left standing in an environment of −20 ° C. for 16 hours was attached to a stainless plate placed parallel to the floor so that the oil-containing resin layer was on the surface, and the adhesion area was 4.9 cm ² . The above-mentioned columnar ice blocks were put on ice.
3. The environment temperature was set to -20 ° C, and three hours after the column-shaped ice blocks were iced, the ice blocks were loaded from the direction parallel to the floor surface in a load cell (DPU-made by Imada Co., Ltd.) in an environment of -20 ° C. 50, the attachment jig A type A-4) was pressed at a speed of 0.1 mm / sec, the load applied during 40 seconds was measured with a force gauge (ZTS-50N manufactured by Imada Co., Ltd.), and the maximum load measured The value obtained by dividing the adhesion area by 4.9 cm ² was recorded as the icing force. The test was performed 3 times and the average value was calculated.
This measurement method was determined with reference to "Study on Snow and Ice Prevention Technology (1st Report), Hokkaido Industrial Test Site Report No.292 (1993)". The icing power increases almost proportionally in response to an increase in the amount of surface oil, at least at -20 ° C.
The evaluation criteria are as follows.
◎ ・ ・ ・ Less than 0.1 N / cm ² ○ ・ ・ ・ 0.1 N / cm ² or more and less than 1.0 N / cm ² × ・ ・ ・ 1.0 N / cm ² or more The smaller the value of icing force is Good, but if less than 1.0 N / cm ² , it is considered to be sufficient for actual use. However, it may be usable even at 1.0 N / cm ² or more.

[Examples 2 to 6 and Reference Examples 1 to 6]
Example 1 is the same as Example 1 except that the mixing ratio of the resin component, the first oil component, and the second oil component was changed when the first paint was produced.

[Example 7]
Example 1 is the same as Example 1 except that the first paint was produced by the following method.
1) First Resin Precursor The same first resin precursor as in Example 1 was used.

2) Oil component As the first oil component, dimethylsiloxane oil (product number KF-96-50CS manufactured by Shin-Etsu Silicone Co., Ltd.), and as the second oil component, carbinol silicone oil (product number KF- manufactured by Shin-Etsu Silicone Co., Ltd.). 6001) was used.

3) Mixing The first resin precursor of 1) and the first oil component and the second oil component of 2) were mixed to obtain a first paint. The blending ratio was 60 wt% for the resin component, 28 wt% for the first oil component, and 12 wt% for the second oil component, based on the total weight of the finally formed oil-containing resin layer.
Here, the value of the solubility parameter of the first oil component, dimethylsiloxane oil, is 11.7, and the value of the solubility parameter of the second oil component, carbinol-modified silicone oil, is 12.2. The dimethylpolysiloxane rubber as a resin component formed by curing the resin precursor has a solubility parameter value of 11.9 (J / cm ³ ) ^1/2 .

[Comparative Example 1]
Example 1 is the same as Example 1 except that the first coating material contains only the first resin precursor and does not contain the oil component.

[Comparative example 2]
Example 1 is the same as Example 1 except that the first paint was produced by the following method.
1) First Resin Precursor The same first resin precursor as in Example 1 was used.

2) Oil component Methylphenylsiloxane oil (Product No. AR-20 manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) is used as the first oil component, and the SP value is different from the first oil component as the second oil component. Methylphenylsiloxane oil (TSF437 manufactured by Momentive) was used.

3) Mixing The first resin precursor of 1) and the first oil component and the second oil component of 2) were mixed in the same manner as in Example 1 to obtain a first coating material. The blending ratio was 25 wt% for the resin component, 56 wt% for the first oil component, and 19 wt% for the second oil component, based on the total weight of the finally formed oil-containing resin layer. The first coating material obtained by the above method was cured in the same manner as in Example 1 to form an oil-containing resin layer having a thickness of about 140 μm, and the oil-containing resin layer was evaluated as follows. It was Here, the value of the solubility parameter of methylphenylsiloxane oil, which is the first oil component, is 12.7 (J / cm ³ ) ^1/2 , and the value of the solubility parameter of methylphenylsiloxane oil, which is the second oil component, is 13. 9 (J / cm ³ ) ^1/2 , and the dimethylpolysiloxane rubber as a resin component formed by curing the above-mentioned first resin precursor has a solubility parameter value of 11.9 (J / cm 3). ³ ) ^1/2 .

The evaluation results are shown in Table 1 below.
Regarding the evaluation of “phase separation and compatibility (change in transmittance, etc.)” in the table, the notation “first oil / second oil” refers to “first oil component” corresponding to a) described above. Of the phase separation and compatibility between the oil and the "second oil component", and the notation "first oil / resin" corresponds to the above-mentioned b) "first oil component" and "oil-containing resin". The expression “second oil / resin”, which has an affinity with the “resin component of the layer”, is between the “second oil component” and the “resin component of the oil-containing resin layer” corresponding to the above c). The respective evaluation results of the affinity of are shown.

Regarding the solubility parameter which is a standard for determining the easiness of mixing the solvent and the solute, in Examples 1 to 6 and Reference Examples 1 to 6, the value of the solubility parameter of the resin component of the oil-containing resin layer and the first oil component Of the solubility parameter of the oil component, that is, | 11.9-11.7 | = 0.2 (J / cm ³ ) ^1/2 , is the difference between the solubility parameter of the resin component of the oil-containing resin layer and the second oil. The difference in the value of the solubility parameter of the component, that is, less than | 11.9-13.9 | = 2.0 (J / cm ³ ) ^1/2 , and the first oil component and the resin of the oil-containing resin layer 11 The difference in solubility parameter between the components, that is, | 11.7-11.9 | = 0.2 (J / cm ³ ) ^1/2 is within 0.6 (J / cm ³ ) ^1/2 It is set.
Similarly, in Example 7, the difference between the solubility parameter value of the resin component of the oil-containing resin layer and the solubility parameter value of the first oil component, that is, | 11.9-11.7 | = 0.2 (J / Cm ³ ) ^1/2 is the difference between the value of the solubility parameter of the resin component of the oil-containing resin layer and the value of the solubility parameter of the second oil component, that is, | 11.9-12.2 | = 0.3 ( J / cm ³ ) ^1/2 and a difference in solubility parameter between the first oil component and the resin component of the oil-containing resin layer 11, that is, | 11.7-11.9 | = 0.2. (J / cm ³ ) ^1/2 is set within 0.6 (J / cm ³ ) ^1/2 .
On the other hand, in Comparative Example 2, the difference between the solubility parameter value of the resin component of the oil-containing resin layer and the solubility parameter value of the first oil component, that is, | 11.9-12.7 | = 0.8 (J / Cm ³ ) ^1/2 is the difference between the value of the solubility parameter of the resin component of the oil-containing resin layer and the value of the solubility parameter of the second oil component, that is, | 11.9-13.9 | = 2.0 ( J / cm ³ ) ^1/2, but a difference in solubility parameter between the first oil component and the resin component of the oil-containing resin layer 11, that is, | 12.7-11.9 | = 0.8 ( J / cm ³ ) ^1/2 is larger than 0.6 (J / cm ³ ) ^1/2 .

With regard to phase separation and compatibility, the transmittance of the mixture of the first oil component and the second oil component changed significantly when the temperature changed from 20 ° C to 3 ° C. It is clear that the second oil component has phase separated.
Since the first oil component does not substantially bleed on the surface of the oil-containing resin layer at both temperatures of 20 ° C. and 3 ° C., it has an affinity for the resin component of the oil-containing resin layer. Can be said. On the other hand, the second oil component does not bleed from the surface of the oil-containing resin layer when the oil-containing resin layer is placed in an environment of 20 ° C, and does not substantially bleed when placed in an environment of 3 ° C. Corresponds to the phase separation between the first oil component and the second oil component, the second oil component changes its behavior in the presence of the first oil component in response to temperature changes. I understand that Furthermore, the second oil component has an affinity for the resin component of the surface resin layer under the environment of 20 ° C., but has an affinity for the resin component of the surface resin layer under the environment of 3 ° C. Does not have. This behavior is also clear from the result of the amount of surface oil.

In the examples, the surface oil amount and the icing force do not become significant at room temperature, for example, 20 ° C., and the surface oil amount at −20 ° C. is 40 μg only when the temperature becomes a predetermined value or less. / Cm ² or more, and as a result, the icing power was less than 1.0. Further, since the oil component bleeding from the oil-containing resin layer 11 is mainly the second oil component of the oil components contained in the oil-containing resin layer, according to this configuration, the oil component is excessive as in the conventional case. The second oil component can be used, for example, to prevent the adhesion of icing snow while preventing unnecessary bleeding.
From the above, the second oil component functions as a low-temperature exudation oil component capable of bleeding (exuding) from the surface of the oil-containing resin layer on the surface resin layer side under the temperature environment where the value is equal to or lower than the predetermined value. I understand that.

In Comparative Example 2, the first oil component and the second oil component do not phase-separate even at a low temperature, and in a temperature environment of a predetermined value or less, the oil component is removed from the surface of the oil-containing resin layer on the surface resin layer side. However, since the first oil component and the second oil component do not phase separate even at low temperatures, it is necessary to contain a large amount of oil component for bleeding. As a result, the abrasion resistance is 100%, and the strength of the oil-containing resin layer cannot be increased. On the other hand, in the oil-containing resin layer produced from the coating material of this example, the first oil component and the second oil component are phase-separated at low temperature, so that even a relatively small amount of oil component bleeds from the surface of the oil-containing resin layer. Therefore, the content of the resin component can be increased, and an oil-containing resin layer having high strength can be realized.

As shown in Example 7, especially when the carbinol-modified silicone oil was used as the second oil component, the icing power was significantly reduced. It is presumed that this is because the wettability to the oil-containing resin layer was improved as compared with the case where phenyl-modified silicone oil was used as the second oil component.

The temperature at which the second oil component is phase-separated from the first oil component, in other words, the temperature at which the surface resin layer bleeds can be adjusted by appropriately selecting the first oil component and the second oil component. As such, the second oil component may function as a cold exudate oil component at various temperatures, for example, at or below freezing and above freezing.

[Examples 8 to 20, Comparative Example 3]
The first paint was prepared in the same manner as in Example 1 except that the types and mixing ratios of the resin component, the first oil component, and the second oil component were changed as shown in Table 2.
Specifically, in all of Examples 8 to 20 and Comparative Example 3, "dimethylpolysiloxane rubber KE-1935"; trade name "KE-1935" (manufactured by Shin-Etsu Silicone Co., Ltd.) was used as the resin component, and As the first oil component, "dimethylsiloxane KF-96 50CS"; trade name "KF-96 50CS" (manufactured by Shin-Etsu Silicone Co., Ltd.) was used.
For the second oil component,
In Examples 8 to 11, "long-chain alkyl-modified siloxane oil KF-4917"; trade name "KF-4917" (manufactured by Shin-Etsu Silicone Co., Ltd.) was used.
In Examples 12, 13, and 17, "epoxy-modified siloxane oil X-22-163"; trade name "X-22-163" (manufactured by Shin-Etsu Silicone Co., Ltd.) was used.
In Examples 14, 15, 19 and 20, "carbinol modified oil KF-6001"; trade name "KF-6001" (manufactured by Shin-Etsu Silicone Co., Ltd.),
In Examples 16 and 18 and Comparative Example 3, "methylphenylsiloxane oil TSF437"; trade name "TSF437" (manufactured by Momentive),
Used respectively.
The evaluation results are shown in Table 2 below.

The following items were further evaluated with respect to Examples and the like.
<Contribution value of dissolution parameter>
The solubility parameter contribution value "F" was calculated by the following formula.
F = f × φ × 100
Here, f is the “contribution value of the solubility parameter” (f _d1 , f _p1 , f _h1 ) of the “molecular unit (compatible molecular unit) that constitutes the monomer structure that is most abundant in the oil-containing resin layer”, "Molecular unit constituting the monomer structure in the second oil component (incompatible molecular unit) having a difference of 0.01 (J / cm ³ ) ^1/2 or more from the solubility parameter of the compatible molecular unit" And the “contribution value of the dissolution parameter” (f _d2 , f _p2 , f _h2 ).
f = ((f _d1 −f _d2 ) ² + (f _p1 −f _p2 ) ² + (f _h1 −f _h2 ) ² ) ^0.5
When there are a plurality of incompatible molecular units, the contribution values are averaged to obtain the above f. Further, the contribution values f _d , f _p , and f _h of the dissolution parameter can be calculated by the following formulas, respectively.
_{f d = δ d / (δ} d + δ p + δ h)
f _p = δ _p / (δ _d + δ _p + δ _h )
_{f h = δ h / (δ} h + δ p + δ h)
Further, φ means the weight fraction of the incompatible component, and can be calculated by the following formula.
φ = (1-gel fraction) × weight ratio of incompatible molecular unit contained in oil component The gel fraction can be determined by the following procedure.
1. The oil-containing resin layer is cut into 2.0 cm × 4.5 cm, and the weight is measured.
2. The oil-containing resin layer is placed in a vial filled with 20 g of toluene and immersed in toluene at room temperature for 24 hours.
3. The oil-containing resin layer is taken out and heated and dried at 150 ° C. for 2 hours with a blow dryer to measure the weight of the residue.
4. The gel fraction is calculated from the following formula.
Gel fraction = residue weight after heat drying (g) / weight of oil-containing resin layer before heat drying (g)
The “weight ratio of incompatible molecular units contained in the oil component” can be calculated by NMR measurement of all oil components including both the first oil component and the second oil component contained in the oil-containing resin layer. it can. All oil components including both the first oil component and the second oil component can be obtained by the following procedure.
1. The oil-containing resin layer is cut into 2.0 × 4.5 cm, placed in a vial filled with 20 g of toluene, and immersed in toluene at room temperature for 24 hours.
2. The oil-containing resin layer is taken out of the vial and dried at 150 ° C. for 12 hours with a blow dryer to obtain a residue. This residue is all the oil components including both the first oil component and the second oil component.

<Wet parameter>
The wetting parameter “Z” is determined by the absolute value of the difference between the value of the solubility parameter of the oil-containing resin layer formed by curing the first resin precursor and the value of the solubility parameter of the second oil component. You can ask. The solubility parameter of the oil-containing resin layer is calculated from the weighted average of the solubility parameters of the resin component, the first oil component, and the second oil component by weight fraction.

<UV resistance>
The UV resistance of the oil-containing resin layer was evaluated as follows.
A super xenon weather meter (model number: SX75, Suga Test Instruments Co., Ltd.) was used as a test device. A test piece film (size: 55 mm × 130 mm) cut to the size of the sample holder was put into a tester and irradiated with ultraviolet rays (wavelength: 300 nm to 400 nm). Regarding the test method, with reference to JIS D0205 Weather resistance test method for automobile parts, the annual average radiant exposure amount of ultraviolet rays (wavelength: 300 nm to 400 nm) was set to 306 kW / m ^2, and this radiant exposure amount was irradiated to the test piece film. As for the test environment temperature, assuming the summer, the test machine environment temperature was 30 ° C., the test piece back surface temperature was 55 ° C., the humidity was 55% RH, and the rotation speed was 1 rotation / min.
The first oil component and the second oil component remaining in the test piece film after ultraviolet irradiation are extracted, and the reduction rate of the second oil component before and after UV irradiation is calculated from the change in the ratio of the first oil component and the second oil component. did. It has been confirmed that the first component oil does not decrease with UV irradiation.
The method for extracting the first oil and the second oil in the film and the method for calculating the reduction rate of the second oil are as follows.
1. The film is cut into 20 mm × 40 mm and placed in a screw tube bottle.
2. Add about 30 g of chloroform to a screw bottle and cap.
3. Using a shaker (Double Action Lab Shaker SRR-2, As One Co., Ltd.), vibrate at 100 rpm for 15 hours to extract the residual oil in the film.
4. Remove any solids left in the screw vial.
5. Chloroform containing the extracted oil is dried in a dryer at 100 ° C. for 2 hours to obtain a mixture of the first oil and the second oil.
6. About 3 mg of the obtained mixture of the first oil and the second oil and about 700 mg of deuterated chloroform are collected in a vial to prepare a mixed solution.
7. Transfer the mixture to an NMR sample tube.
8. 1H NMR is measured by NMR (model number: ULTRASHIELD 300, manufactured by BRUKER), and attribution is based on the molecular structures of various second component oils.
9. The decrease rate of the second component oil due to UV irradiation is calculated from the change in the H number of Si—CH ₃ before and after UV irradiation.

The evaluation criteria are as follows.
1 ... 2nd component oil reduction rate less than 10% 2 ... 2nd component oil reduction rate 10 to less than 30% 3 ... 2nd component oil reduction rate 30 to less than 50%

<Water resistance>
The water resistance of the oil-containing resin layer was evaluated as follows.
A rain tester (manufactured by Nishiyama Seisakusho) was used as a test device. A test piece film (size: 150 mm × 150 mm) was put in, and an amount equivalent to the annual precipitation was rained from the upper part of the film. The annual precipitation was set to 1600 mm with reference to the data of the Japan Meteorological Agency. As for the test environment temperature, assuming a rainy day in winter, the test machine environment temperature was 5 ° C, the precipitation temperature was 5 ° C, and the rainfall rate was about 500 mm / h.
The first oil component and the second oil component remaining in the test piece film after the water resistance test are extracted, and the reduction rate of the second oil component before and after the water resistance test is calculated from the change in the ratio of the first oil component and the second oil component. did. It has been confirmed that the first component oil does not decrease in the water resistance test.
The method of extracting the first oil and the second oil in the film, the method of calculating the reduction rate of the second oil, and the evaluation criteria were the same as those in the above <UV resistance>.
The evaluation results are shown in Table 3 below. For convenience, Table 3 also shows the composition of the oil-containing resin layer, that is, the resin component, the first oil component, and the second oil component.

<Amount of oil that gives an icing power of 0.15 N / cm ² >
By changing the ratio of the first oil component and the second oil component while maintaining only the resin component of the resin component, the first oil component, and the second oil component at a predetermined blending ratio (wt%), The amount of oil that gives an icing force of 0.15 N / cm ² was estimated. The results are shown in Table 4 below. As in Table 3, Table 4 also shows the composition of the oil-containing resin layer, that is, the resin component, the first oil component, and the second oil component.

As is clear from the above results, when a long-chain alkyl-modified siloxane oil or carbinol-modified silicone oil is used as the second oil component, a low icing power, that is, a high icing power is obtained even with a small oil amount of 50 μg / cm ^2. It has been found to exhibit anti-icing properties.

As described above, according to the present invention, a product capable of preventing icing and / or snow accretion, particularly a paint that can be used in a more flexible manner than a sheet or the like having a fixed shape from the beginning of use. And a film is provided.

It should be understood that the above description is of the preferred embodiment and is merely representative of the article. It can be appreciated that variations and modifications of the different embodiments will be readily apparent to those skilled in the art in light of the above teachings. Accordingly, the exemplary and alternative embodiments can be made without departing from the spirit of the article as set forth in the appended claims.

10 structure 11 oil-containing resin layer 12 surface resin layer

Claims (27)

1. The first oil component,
   A second oil component,
   A first resin precursor which is a precursor of a resin component;
   Including,
   A paint for forming an oil-containing resin layer containing the first and second oil components and the resin component by curing the first resin precursor containing the first and second oil components. hand,
   The second oil component constitutes a low temperature phase-separable oil component capable of phase-separating from the first oil component and leaching from the oil-containing resin layer when the temperature drops below a predetermined value. Paint to do.
2. The paint according to claim 1, wherein the first and second oil components are values of a solubility parameter of a resin component of the oil-containing resin layer formed by curing the first resin precursor. The difference between the (SP value) and the solubility parameter value of the first oil component is the difference between the solubility parameter value (SP value) of the resin component of the oil-containing resin layer and the solubility parameter value of the second oil component. Paint that is smaller than the difference.
3. The paint according to claim 1 or 2, wherein the first resin precursor is a moisture-curable type that is cured by moisture.
4. The paint according to claim 1 or 2, wherein the first resin precursor is an ultraviolet curable type that is cured by irradiation with ultraviolet rays.
5. The paint according to claim 1 or 2, wherein the first resin precursor is a thermosetting type that is cured by heating.
6. The coating material according to claim 1 or 2, wherein the first resin precursor is cured by adding a curing agent that causes a crosslinking reaction with the first resin precursor. paint.
7. A combination of the coating composition according to claim 6 and a liquid curing agent that cures the first resin precursor by a crosslinking reaction with the first resin precursor of the coating composition.
8. The paint according to any one of claims 1 to 7,
   A coating material containing 25 wt% or more of a resin component of the oil-containing resin layer based on the weight of the entire oil-containing resin layer.
9. It is the paint according to claim 8,
   A coating material comprising the second oil component in a proportion of 3 wt% or more based on the total weight of the oil-containing resin layer.
10. The paint according to any one of claims 1 to 9,
    A second resin precursor that forms a surface resin layer by being cured on the oil-containing resin layer formed by curing the first resin precursor;
    Further including,
    The surface resin layer has an oil permeability that allows the low-temperature phase-separable oil component exuded from the oil-containing resin layer to permeate to the surface of the surface resin layer on the side opposite to the oil-containing resin layer. A paint characterized by.
11. The paint according to claim 10, wherein the surface resin layer has higher abrasion resistance than the oil-containing resin layer.
12. The paint according to any one of claims 1 to 11, wherein the amount of surface oil at -20 ° C is 40 µg / cm ² or more.
13. A paint as claimed in any one of claims 1 to 12, the difference in solubility parameter 0.6 (J / cm ³⁾ between the resin component of the first oil component the oil-containing resin layer 1 ^/ A paint characterized by being within ² .
14. The paint according to any one of claims 1 to 13, wherein the predetermined value is a freezing point.
15. The paint according to any one of claims 1 to 12,
    Absolute value of the difference between the solubility parameter value (SP value) of the oil-containing resin layer formed by curing the first resin precursor and the solubility parameter value (SP value) of the second oil component. A coating material having a wetting parameter of 1.5 (J / cm ³ ) ^1/2 or less, which is obtained in ¹ .
16. The paint according to any one of claims 1 to 12,
    A coating material, wherein the oil-containing resin layer formed by curing the first resin precursor has a solubility parameter contribution value of 0.1 or more.
17. A film having an oil-containing resin layer containing first and second oil components,
    The second oil component constitutes a low temperature phase-separable oil component capable of phase-separating from the first oil component and leaching from the oil-containing resin layer when the temperature drops below a predetermined value. A film to do.
18. The film according to claim 17, wherein the first and second oil components have a solubility parameter value (SP value) of a resin component of the oil-containing resin layer and a solubility parameter value of the first oil component ( The difference with the SP value) is smaller than the difference between the solubility parameter value (SP value) of the resin component of the oil-containing resin layer and the solubility parameter value (SP value) of the second oil component. A film to do.
19. The film according to claim 17 or 18, wherein
    A film comprising the resin component of the oil-containing resin layer in an amount of 25 wt% or more based on the total weight of the oil-containing resin layer.
20. The paint according to claim 19,
    A film comprising the second oil component in a proportion of 3 wt% or more based on the total weight of the oil-containing resin layer.
21. The film according to any one of claims 17 to 20, wherein
    Further comprising a surface resin layer on the oil-containing resin layer,
    The surface resin layer has an oil permeability that allows the low-temperature phase-separable oil component exuded from the oil-containing resin layer to permeate to the surface of the surface resin layer on the side opposite to the oil-containing resin layer. A film characterized by.
22. The film according to claim 21, wherein the surface resin layer has higher abrasion resistance than the oil-containing resin layer.
23. The paint according to any one of claims 17 to 22, wherein the amount of surface oil at -20 ° C is 40 µg / cm ² or more.
24. The film according to any one of claims 17 to 23, wherein a difference in solubility parameter between the first oil component and the resin component of the oil-containing resin layer is 0.6 (J / cm ³ ) ^{1 /} A film characterized by being within ² .
25. The film according to any one of claims 17 to 24, wherein the predetermined value is a freezing point.
26. The film according to any one of claims 17 to 25,
    The wetting parameter, which is obtained by the absolute value of the difference between the solubility parameter value (SP value) of the oil-containing resin layer and the solubility parameter value (SP value) of the second oil component, is 1.5 (J / cm ³ ). A film characterized by being ^1/2 or less.
27. The film according to any one of claims 17 to 26,
    A film, wherein the oil-containing resin layer has a solubility parameter contribution value of 0.1 or more.

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